Extreme pressure lubricants



Patented July 13, 1954 EXTREME PRESSURE LUBRICANTS Roy E.

Bell, Concord,

Thorpe, San Francisco, and Edward R.

Calif., assignors to Shell Development Company, Emeryville, Califl, a corporation of Delaware No Drawing. Application August 18, 1951, Serial No. 242,584

17 Claims.

This invention relates to lubricants particularly suitable for lubrication under extreme operating conditions such as under extreme Wear conditions.

It is well known that the high pressure occurring in certain types of gears and bearings may cause a film of lubricant to rupture with consequent damage to the machinery. It has been shown that base lubricants such as mineral oil and/or synthetic oil can be improved with regard to their protective effect particularly on rubbing surfaces by the addition of certain substances, so that excessive wear, scufling and seizure, which normally follow a break in the film of lubricant, can thus be prevented even under the most adverse pressure and speed conditions. Lubricants possessing this highly desirable property are called extreme pressure lubricants.

It is known that certain elements or compounds of elements of the type of chlorine, sulfur, and lead are capable of imparting extreme properties to lubricants, which may be lubricating oils and greases, when blended therewith. Among the compounds heretofore used are notably the lead soaps, free or loosely bound sulfur, and certain chlorinated organic compounds. A principal objection to extreme pressure compounds of this latter class is that they are highly reactive with contacting surfaces causing pitting, corrosion and discoloration of said surfaces. Also the load-carrying capacities obtained with such lubricants are oftentimes inadequate for modern truck and automotive hypoid gear applications. treme pressure agents is that they alter the original chemical nature of the contacting surface which is undesirable. Additionally, because of the activity of agents of the type under discussion they deplete rapidly, resulting in at the very best, only a temporary solution to extreme pressure lubrication.

It has now been discovered that improved extreme pressure lubricants can be obtained by incorporating with a base lubricant a minor amount of oil soluble secondary amine salt of a polyhalohydrocarbon phosphonic or phosphinic acid compound represented by the general formula X X),..R Ry A wherein A is an oil-soluble secondary amine,

preferably a secondary aliphatic amine having Another objection to reactive exat least 10 carbon atoms; the Xs can be the same or difierent divalent atoms of a non-metallic element of group VI B of the periodic table of the elements; R represents a halogen-substituted hydrocarbyl radical, preferably a polyhaloalkane radical in which at leastone of the halogen atoms is not more than four carbon atoms removed from the phosphorus atom and particularly preferred compounds are'those wherein R represents the trihalomethyl, more specifically and preferred the trichloromethyl (CC13) radical; R is hydrogen or an unsubstituted or a polar substituted [CN, SeN, 0R Cl, NO, N02, NR 503R (R. is hydrogen or the hydrogen equivalent of a non-ash forming cationic group e. g. amines) etc.], saturated or unsaturated hydrocarbon radical selected from the class consisting of alkyl, aryl, aralkyl, alkaryl, cycloalkyl radicals; and m is 0 or 1.

THE CATION PORTION The cation portion of salts of this invention include secondary amines preferably aliphatic and cycloaliphatic amines, containing from 10 to .36 carbon atoms. Illustrative of such amines are diamyl amine, dihexylamine, di(2-ethylhexyl) amine, dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecyla mine, dioctadecyl amine, dibromodioctadecylamine, N-isopropyloleylamine, diricinoleylamine, N-butylricinoleylamine, N-butyl 2 ethylhexyl amine, dilaurylolamine, N-methyloleylamine, N- ethyloctylamine, N-isoamyl hexylamine; dicyclohexylamine, dicyclopentylamine, N-cyclohexyloctylamine cyclohexylbenzylamine; cycloaliphatic, N-benzyloctylamine, N-benzyl-2-ethylhexylamine, N-allyloctylamine, N-dodecyl-2- ethylhexylamine, N- l-isobutyl-3-methy1butyl) 3,3,5-methylcyclohexylamine, di(l isobutyl 3- methyl-butyl) amine; N n dodecyl diethylene triamine, N-n-tetradecyldiethylene triamine, N- octylethylene diamine, N-Z-ethylhexyl N-hexadecyl triethylene tetramine, N-heptyl trimethylene diamine, N-tetradecyl tripropylene tetramine, N,N'-diallyl trimethylene diamine, N-butyl morpholine, N-(para-hydroxyphenol) morpholine, N-Z-ethyl hexylmorpholine, and the like.

THE ACID PORTION The acid portion of amine salts of this invention includes the polyhalo-organo and preferably the polyhaloalkane dibasic phosphonic "acids, which can be prepared by oxidation of a suitable primary organo phosphine or by hydrolysis of oxyhalo phosphines or preferably by pyrolyzing a dihydrocarbyl haloalkanephosphonate, preferably a lower di-n-alkyl or a lower di-sec-alkyl polyhaloalkane phosphonate, by heating at about 160 C. to about 225 C. in a liquid phase while withdrawing evolved gases. The pyrolysis is preferably carried out in the presence of acid and in the liquid phase. The presence of acid in the products undergoing pyrolysis, such as strong non-volatile mineral acid, accelerates the pyrolysis reaction. The non-gaseous products of the pyrolysis can be worked up by dissolving in an inert organic solvent, such as petroleum ether, acetone, amyl propionate or benzene, and the dibasic phosphonic acid recovered from the solution by precipitation as an insoluble salt, such as the silver salt, and reconverted to the acid by treatment with a strong mineral acid, such as hydrochloric acid. The crude dibasic phosphonic acid can be purified by recrystallization, preferably from concentrated nitric or hydrochloric acid solution, by distillation in vacuo, or by other suitable means. Non-catalytic pyrolysis of the di-n-alkyl esters is carried out at substantially atmospheric pressures and at temperatures of from about 160 C. to about 350 C. Lower temperatures, down to about 100 C. can be used with di-sec.-alkyl esters. In addition, the haloalkanephosphonic acids can be prepared from the corresponding full esters by hydrolysis or by treating the full esters in the presence of HBr at an elevated temperature.

The monoesters of the above dibasic phosphonic acids can be prepared by a transesterification reaction between a dibasic phosphonic acid having a halogen-substituted aliphatic radical directly linked by a carbon-to-phosphorus bond to the phosphorus atom of the phosphono group with a diester of said phosphonic acid. The transesterification reaction can be efiected by heating a mixture of the dibasic phosphonic acid and the diester of a phosphonic acid at elevated temperatures, in the presence of esterification catalysts if desired. Temperatures of from about 35 C. to about 200 C. can be employed, a preferred range being from about 50 C. to about 135 C. The ratio between the amount of the diester and of the dibasic acid initially present in the mixture can be varied, say from about 1 to 10:1, expressed on a mole basis. Substantially equimolar proportions are preferred. The reaction can be conducted in the presence of inert solvents, if desired, such as a petroleum solvent,

e. g., petroleum ether, a ketone solvent, e. g., cyclohexanone, or dioctyl ketone, an ether, such as diisoamyl ether of dioxane, or the like. Superatmospheric pressures can be employed. The reaction between the dibasic phosphonic acid and the diester can be carried out either in a b'atchwise manner or, especially in larger scale operations, by a continuous process.

The reaction between the dibasic phosphonic acid and the diester appears to be one that leads to the formation of an equilibrium mixture comprising the desired monobasic phosphonic acid and the selected reactants. The time required in any specific case for attainment of the equilibrium depends upon whether or not catalysts are used, upon the specific reactants that are involved and upon the reaction temperature. In general, reaction times of from about 1 hour to 150 or more hours are used. As the reaction progresses, the content of strong acid in the reaction mixture increases. The extent of the reaction can be estimated and followed by titration of aliquots of the reaction mixture. Yields of the monobasic halogen-substituted organo and preferably aliphatic phosphonic acid as high as based on the amounts of the reactants consumed, can be attained. By intermittently or continuously removing the monobasic halogen-substituted aliphatic phosphonic acid from the mixture, and recycling unconsumed reactants, equally high conversions of the reactants to desired product are realized.

The desired monobasic phosphonic acid ester can be recovered from the reaction mixture by any suitable method, including, without being limited thereto, extraction of the mixture with selective solvents, fractional distillation, and crystallization from solvents.

It will be appreciated that the desired monobasic phosphonic acid ester can be prepared directly by reaction between the corresponding halogen-substituted dibasic phosphonic acid and the diester of the selected alcohol with the dibasic phosphonic acid, or that in some cases an indirect procedure can be utilized. For example, 2,3- dichloropropyl trichloromethanephosphonic acid is prepared directly by reaction between trichloromethanephopshonic acid and bis-(2,3- dichloropropyl) trichloromethanephosphonate, or it is prepared by first reacting in the abovedescribed manner trichloromethanephosphonic acid with diallyl trichloromethane phosphonate to produce allyl trichloromethanephosphonic acid partial ester, separating out this product, and then chlorinating it to obtain the desired 2,3- dichloropropyl trichloromethanephosphonic acid partial ester. In other cases, the phosphonic acids of the invention in which the esterifying radical is halogen-substituted can be prepared by substitutive halogenation of corresponding phosphonic acids in which the esterifying alcohol radical is the radical of saturated unsubstituted alcohol. The choice between the direct and the indirect methods will ordinarily depend upon whether reactive groups which interfere with the transesterification reaction are present in the alcohol radical of the phosphonic acid diester, upon the availability of the phosphonic acid diester required for direct production of the desired monobasic phopshonic acid, and upon other similar considerations.

If the half ester is prepared from the dialkyl phosphonate by direct pyrolysis, the reaction is initiated at about C. Pyrolysis is efiected at a somewhat lower temperature thereafter and the reaction mixture is cooled rapidly when it becomes apparent that pyrolysis to the half ester is essentially complete.

Ammonium or amine salts of mixtures of the dibasic phosphonic acids and monoesters thereof as defined above and specifically illustrated hereinafter can be used in the practice of the invention. If desired, the amines can be used in excess of as much as 50% when forming salts of this invention.

The following examples will serve to illustrate methods of preparing the acid portion of amine salts of this invention. It is to be understood that the examples are presented with the intent of illustrating selected specific aspects of the invention and not with the intent of limiting the invention other than as it is defined in the hereto-appended claims. In the examples the parts are parts by weight unless specified otherwise.

PREPARATION OF THE ACID PORTION phite with carbon tetrachloride is heated at 180 C. in a glass vessel open to the atmosphere. During the heating, gas is evolved; a collected sample is found to be largely butylene. The heating is continued until the material in the kettle turns solid. The solid product is purified by extraction of soluble materials in carbon tetrachloride. 'The portion remaining after the extraction is found by analysis to be better than 90% pure trichloromethanephosphonic acid.

Example II .-Preparation of butyl trichloromethanephosphonic acid Triohloromethanephosphonic acid prepared as above was dissolved in an equimolar amount of di-butyl trichloromethanephosphonate and the mixture heated at 100 C. for 32.5 hours. During the heating period small samples of the mixture were withdrawn at intervals, dissolved in a solvent mixture composed of 50% by volume benzene, 40.5% by volume isopropyl alcohol, and 0.5% by volume water, and titrated with a standardized approximately 0.1 N solution of KOH in isopropyl alcohol. The titration showed that as the heating progressed there occurred a gradual disappearance of the weak acid group of the trichloromethanephosphonic acid and an increase in the amount of strong acid present. At 32.5 hours, the reaction was indicated to be complete. The crude reaction mixture thus prepared was extracted with a solution of sodium hydroxide in water in an amount equivalent to the acid content of the mixture. The aqueous solution then was extracted with benzene and with ethyl ether and decolorized by treatment with activated carbon. The butyl trichloromethanephosphonic acid partial ester was sprung by addition of 6 moles hydrochloric acid to the aqueous solution and was extracted from the solution with diethyl ether. The diethyl ether was flashed from the extract and the residue was topped in a molecular still with the thimble at 36 C. The bottoms fraction was found by potentiometric titration to contain 78% by weight of butyl trichloromethanephosphonic acid mono-ester along with minor amounts of trichloromethanephosphonic acid and di-butyl trichloromethanephosphonate. The bottoms had the following composition: 23.5% carbon; 4.6% hydrogen; 11.9% phosphorus; 37.9% chlorine.

Example III.Preparaticm of butyl trichloromethanephosphonic acid Per cent Dibutyl trichloromethanephosphonate 1'7 Butyl trichloromethanephosphonic acid 56 Trichloromethanephosphonic acid 2'? Example W A crude dibutyl trichloromethanephosphonate (Cl=26.6%) was heated to algettle temperature of 160 C. until 50-60% ofthe theoretical of 1 equivalent butylene was evolved and on analysis a product was obtained containing:

Per cent Trichloromethanephosphonic acid 7 Butyl trichloromethanephosphonic acid 60 Dibutyl trichloromethanephosphonic acid 23 Extraneous matter 20 Properties of said mixture:

. O Sp. gr. C 1.05 Visc. at F., 08 1000 Vise. at 210 F., 08 65-70 Other suitable and effective illustrative examples of polyhaloalkane phosphonic acids which are convertible to amine salts and/or their partial esters and then to the amine salts applicable to the practice of the present invention and which can be represented by the formula:

XH (II) wherein R and X are the same as in Formula I, are as follows:

Polyhalo-organophosphinic acids within the purview of the invention and of Formula I can be represented by the general formula:

wherein R, R and X are the same as in Formula I.

The phosphinic acids are prepared by addition of sodium hypophosphite to unsaturated organic compounds followed by acidification, as illustrated in the following examples.

Example V.-Preparation of dichloro-octanephosphinic acid About equimols of sodium hypophosphite and dichlorooctene were added to methanol containing a catalytic amount of 2,2-bis-(tert.-butyl peroxy) butane and the mixture reacted in an enclosed pressure-resistant vessel at a temperature of about C. to C. for about two 0 hours under agitation. At the end of the reaction, a single liquid phase was observed which was sodium dichlorooctane phosphinate dissolved in the methanol; acidification yielded dichlorooctanephosphinic acid.

Other illustrative examples of suitable and eifective polyhaloalkanephosphinic acids for use in the practice of the invention are:

Trichloromethanephosphinic acid Tribromomethanephosphinic acid Benzenetrichloromethanephosphinic acid The preferred monoesters of phosphonic acids as defined above are the trihalomethanephos- 7 phonic acid monoesters and can be represented by the formula:

in which Hal represents halogen, preferably chlorine and bromine and X and R are the same as in Formula I. Particularly preferred monobasic trihalomethanephosphonic acid monoesters are:

n-Propyl trichloromethanephosphonic acid Methyl trichloromethanephosphonic acid Ethyl trichloromethanephosphonic acid Isopropyl trichloromethanephosphonic acid n-Hexyl trichloromethanephosphonic acid n-Butyl trichloromethanephosphonic acid Decyl trichloromethanephosphonic acid Chlorophenyl trichloromethanephosphonic acid Tetradecyl trichloromethanephosphonic acid Methallyl trichloromethanephosphonic acid Benzyl trichloromethanephosphonic acid Bis (chloromethyl) methyl trichloromethancphosphonic acid Ethylene bis(trichloromethanephosphonic) acid Isoamyl trichloromethanephosphonic acid Octyl trichloromethanephosphonic acid Chlorophenyl trichloromethanephosphonic acid Dodecyl triohloromethanephosphonic acid Hexadecyl trichloromethanephosphonic acid Phenyl trichloromethanephosphonic acid Benzyl trichloromethanephosphonic acid Octadecyl trichloromethanephosphonic acid Allyl trichloromethanephosphonic acid Crotyl trichloromethanephosphonic acid Cinnamyl trichloromethanephosphonic acid Propargyl trichloromethanephosphonic acid 3-chloroallyl trichloromethanephosphonic acid Oleyl trichloromethanephosphonic acid 3 amylmercaptopropyl trichloromethanephosphonic acid 3-ethoxypropyl trichloromethanephosphonic acid Bis (chloromethyl) methyl trichloromethanephosphonic acid 3-aminopropyl tribromomethanephosphonic acid Ethylene bis(trichloromethanephosphonic) acid 3 hydroxypropyl trichloromethanephosphonic acid Cyclohexyl trichloromethanephosphonic acid 2-chloroal1y1 trichloromethanephosphonic acid Butyl dibromochloromethanephosphonic acid Isoamyl trifluoromethanephosphonic acid Ethyl triiodomethanephosphonic acid n-Butyl fluorodichloromethanephosphonic acid Still other monobasic phosphonic acids suitable as additive agents are:

Butyl 3-bromopropanephosphonic acid Ethyl 2,3-dibromopropanephosphonic acid Isopropyl 1,3,5-trichlorohexanephosphonic acid Cyanoethyl 1,1,4-tribromobutanephosphonic acid Methoxyethyl 1 bromopropane 2 phosphonic acid.

3 thiocyanopropyl 1,1,3 trichlorobutanephosphonic acid Allyl 1,1-dichloroethanephosphonic acid Hexyl 1,1-dichloroethanephosphonic acid Butyl 3-bromo-2-propene-l-phosphonic acid Cyclohexyl 3-bromo-2-fiuoropropanephosphonic acid n-Butyl fiuoromethanephosphonic acid Allyl tri-2-fiuoro-l-chloroethanephosphonic acid Ethyl 1,1,3-trichlorononanephosphonic acid Butyl iodomethanephosphonic acid Butyl B-bromopropanephosphonic acid Isobutyl 2- (chloromethyl) propane-2-phosphonic acid 2 carbomethoxyethyl 2,3 dichloropropanephosphonic acid Butyl trichloromethanetrithiophosphonic acid Allyl 1,1,2 trichloroethanedithiolophosphonic acid Butyl tribromomethanethionophosphonic acid Butyl trichloromethanetriselenophosphonic acid Ammonium or amine salts prepared from mixtures of the monobasic phosphonic acids with free phosphonic acids or with free phosphonic and /or phosphinic acids can be used. When mixtures are used, the monobasic phosphonic acid is present in the predominant amount preferably at least 50% of the mixture. The following are illustrative suitable mixtures in which the monobasic acid is present in at least 50 to of the mixture:

THE AMMONIUM OR AMINE SALTS The ammonium salts of the acidic phosphono compounds and mixtures thereof as described can be prepared by reacting if desired in a solvent or in presence of water and under suitable conditions such as mixing at room temperature, stirring or heating selected amines with polyhalo organo phosphorus compounds as described above. Salts produced in the foregoing or equivalent manner can be purified by recrystallization from suitable solvents or other applicable procedure which will be apparent to those skilled in the art.

Example VI.-Di-2-ethylhexylammonium butyl trichloromethanephosphonate In a suitable vessel butyl trichloromethanephosphonate was reacted at a temperature of around 50 C. with di-2-ethylhexylammonium in an amount sufficient to neutralize the total acidity of the butyl trichloromethanephosphonate. The product formed was the completely neutralized di-Z-ethylhexylammonium butyl trichloromethanephosphonate which was oil soluble and had good extreme pressure properties.

Example VII .Di-2-ethylhe:rylammonium salt of pyrolyzed product of Example IV To di-Z-ethylhexylammonium was added slowly with agitation the pyrolyzed product of Example IV and the mixture was cooled by ice water so as to keep the temperature below 50 C. The reactants were in such proportions so that the amine was in just suflicient amount to neutralize the total acidity of the pyrolysis product. The ammonium salt was oil soluble, had good extreme pressure properties and had the following additional properties:

Sp. gr. 20/4 1.0463

Visc. at F. (05.) 1013 Visc. at 210 F. (cs.) 67.3 Chlorine, percent w 15.3

Example VIII .Dioctadecylammomum butyl trichloromethanephosphmzate Example IX.Di(1-isobatyl-3-meth'ylbutyl) ammonium salt of butyl trichloromethanephosphonic acid This salt is prepared by neutralizing butyl trichloromethanephosphonic acid with the theoretically required amount of di(1-isobutyl-3-methyl butyl) ammonium under conditions as described in Example VIII to produce an oil-soluble di(1- isobutyl-B-methylbutyl) ammonium butyl trichloromethanephosphonate.

Example X.Di-2-ethylhexylammonium salt of dichloro-octane phosphinzc acid This salt is prepared by neutralizing dichlorooctane phosphinic acid with the theoretically required amount of di-2-ethylhexylammonium under conditions described in Example VII to produce an oil-soluble di-2-ethyl hexylammonium salt of dichloro-octane phosphonic acid.

Example XI .Dz'-2-ethylhexylammonium salt of octyl trichloromethanephosphonic ac d This salt was prepared under substantially the same conditions as described in Example VII to produce an oil-soluble salt of di-2-ethyl hexylammonium and octyl trichloromethanephosphonic acid.

Example XII.-Dicyclohexylammoniam salt of butyl trifluoromethanephosphonic acid This salt is prepared by neutralizing butyl trifiuoromethanephosphonic acid with the theoretically required amount of dicyclohexylammonium to produce an oil-soluble dicyclohexylammonium butyl trifiuoromethanephosphonate.

Example XIII.-N-butyl-2-ethylhexylammo'nium salt of allyl trichloromethanephosphom'c acid This salt is prepared by neutralizing allyl trichloromethanephosphonic acid with the theoretically required amount of N-butyl-2-ethylhexylammonium to produce N-butyl-2-ethylhexylammonium allyl trichloromethanephosphonate.

Example XIV.--N methyloctadecylammom'um salt of Z-hydroxyethyl trichloromethanephosphom'c acid Thi salt is prepared under conditions described in Example VII to produce an oil-soluble N-methyloctadecylammonium salt of Z-hydroxyethyl trichloromethanephosphonic acid.

Example XV.-N-benzyl-2-ethylhe:vylammonium salt of isoamyl trichloromethanephosphom'c acid Thi salt is prepared under conditions described in Example VII to produce an oil-soluble N-benzyl-Z-ethylhexylammonium salt of isoamyl trichloromethanephosphonic acid.

Other illustrative examples of ammonium salts for use in the practice of this invention are:

Di-z-ethylhexylammonium salt of dichloroethanephosphonic acid 10 Di-Z-ethylhexylammonium salt of dichloroethanethiophosphonic acid Di-Z-ethylhexylammonium salt of dibromobutanephosphonic acid Di-Z-ethylhexylammonium salt of trichlorobenzenep-hosphonic acid Di-Z-ethylhexylammonium salt of phenyl trichloromethanephosphonic acid Di-2-ethylhexylammonium salt of n-hexyl trichloromethanephosphonic acid Di-Z-ethylhexylammonium salt of chlorophenyl trichlorometha'nephosphonic acid Di-2-ethylhexylammonium salt of hexadecyl phosphonic acid Di-z-ethylhexylammonium phonic acid Di-Z-ethylhexylammonium phonic acid Di-Z-ethylhexylammonium propanephosphonic acid Di-Z-ethylhexylammonium salt of Cyclohexyl 3- bromo-2-fiuoropropanephosphonic acid Di-Z-ethylhexylammonium salt of butyl trichloromethanetrithiophosphonic acid Cyclohexyl benzyl ammonium salt of dichlorocthanephosphonic acid Cyclohexyl benzyl ammonium salt of dibromobutanephosphonic acid Cyclohexylbenzyl ammonium salt of n-hexyl trichloromethanephosphonic acid Cyclohexyl benzyl ammonium salt of chlorophenyl trichloromethanephosphonic acid Cyclohexyl benzyl ammonium salt of ally1 phosphonic acid Cyclohexyl benzyl ammonium salt of 2,3-dibromopropane phosphonic acid Cyclohexyl benzyl ammonium salt of butyl trichloromethanetrithiophosphonic acid Dihexadecyl ammonium salt of dichloroethane thiophosphonic acid Dihexadecyl ammonium salt of trichlorobenzene phosphonic acid Dihexadecyl ammonium salt of n-hexyltrichloromethane phosphonic acid Dihexadecyl ammonium salt of chlorophenyl trichloromethanephosphonic acid N-ethyl octylammonium salt of dichloroethane phosphonic acid N-ethyl octylammonium salt of benzene trichloromethanephosphonic acid N-ethyl octylammonium salt of n-hexyltrichloromethanephosphonic acid N-ethyl octylammonium salt of chlorophenyl trichloromethanephosphonic acid Dodecyl-Z-ethylhexylammonium salt of dichloroethane thiophosphonic acid Dodecyl-2-ethylhexylammonium salt of benzene trichloromethane phosphonic acid Dodecyl-2-ethylhexylammonium salt of n-hexyltrichloromethane phosphonic acid Dodecyl-2-ethylhexylammonium salt of butyl trichloromethane trithiophosphonic acid isobutyl 3 methylbutyl 3,3,5 methyl cyclohexylammonium salt of dibromobutane phosphonic acid isobutyl 3 methylbutyl 3,3,5 methyl cyclohexylammonium salt of trichlorobenzene phosphonic acid isobutyl 3 methylbutyl 3,3,5 methyl cyclohexylammonium salt of chlorophenyl trichloromethane phosphonic acid Dicyclopentylammonium salt of allyl phosphonic acid Dioctylammonium salt of dichloroethane phosphonic acid salt of allyl phossalt of oleyl phossalt of 2,3-dibromotri- In addition to the above specific ammonium salts any of the amines and mixtures thereof can be used to form salts with any of the acids disclosed above.

The ammonium or amine salts and mixtures thereof of this invention can be used in a suitable oily medium in amounts ranging from 0.001% to 20% and preferably from 0.01% to by weight, based on the weight of the total composition.

The salts of this invention in addition to being capable of imparting extreme pressure properties to base lubricants, e. g., gear oils, lubricating oils, etc., can be used to improve the properties of liquids and/or solids suitable for use as cutting fluids, hydraulic fluids, rust and corrosion-inhibiting compositions, coating compositions, greases, fuels and the like. More particularly this invention pertains to lubricants such as natural and/or synthetic lubricants, emulsions, aqueous solutions and organic and/or inorganic materials which can be adapted for lubricating purposes.

The additive combination is particularly suitable for use in gasoline, kerosene, hydrocarbon fuel oil, gas oil, turbine oil, motor oil, mineral spirits, aromatic solvents, petroleum lubricating oils which may or may not be refined as by solvent extraction, and treatment, etc., and which may be soap thickened to form greases, petrolatum, paraflin waxes, albino asphalts, etc.

Also, synthetic oils may be used as the vehicles, such as polymerized olefins, polymers and copolymers of alkylene glycols and alkylene oxides; organic esters, e. g. 2-ethylhexyl sebacate, allyl laurate, and polymers thereof; dioctyl phthalate, trioctyl phosphate, polymeric tetrahydrofuran, polyalkyl siloxanes and silicates, and the like. Mixtures of synthetic and natural lubricants and oils may be used. In addition, resinous materials such as petroleum resins, natural resins as rosin, resins formed by polymerization of drying fatty oils, phenol-formaldehyde resins, glyptal-typc resins formed by esterification of polyhydric alcohols with polycarboxylic acids can be used.

Still other classes of vehicles are aqueous lubricants, including water-in-oil and oil-in-water emulsions suitable for various uses such as lubrieating, cooling, rust-inhibiting, and the like, as well as hydraulic fluids, heat transfer fluids, fireproofing compositions, agricultural agents such as insecticides, fungicides, etc.

Compositions of this invention were evaluated as extreme pressure agents by use of the Four- Ball Extreme Pressure Lubricating Tester similar in principle to the Boerlage apparatus described in the magazine, Engineering, volume 5 136, July 13, 1933. This apparatus comprises four steel balls arranged in a pyramid formation. The top ball is rotated by s indles against the three bottom balls which are clamped in a stationary ball holder. The balls are immersed in the composition to be tested. Tests were run under conditions indicated in the following table and compared with other outstanding extreme pressure compounds.

Four-ball evaluation of EP compositions [1020 R. P. M.; 1 minute, steel on steel, ambient. temperature] Amount, Initial Base Oil Additive Percent Seizure \VL. Loud, Kg.

A 1 X 1. 170-180 A Ex. XII 1.0 170-180 A Dihexylammonium salt of 1.0 170-180 butyl trichloromethanc phosphonic acid. B do 1.0 170-180 A-SAE 00 mineral lubricating oil; BSAE 30 mineral lubrieating oil; C-SAE low mineral lubricating oil: D$yn1l1elie lubricant (di-Z-ethylhcxy] sebacate).

THERMAL STABILITY TEST Compositions of this invention were also eval- Speed: 3000 R. P. M. Test duration: 5 mms. running at each load Specimen: Involute spur gear (SAE 3312 steel) Composition: Score load (lbs.) Mineral oil 5 Mineral oil+1% of additive of Ex. VI 85 Compositions of this invention were also tested in the hypoid gear machine which essentially is built on the four-square (closed power circuit) principle. The first two corners of the square are formed by commercial hypoid gears and the other two by helical gears. A pair of helical gears placed on a common shaft and mating with the corner gears can be moved by hydraulic pressure along the shaft axis. This movement, which can be accomplished while the machine is running, produces torque in the system, proportional to the hydraulic pressure. The machine is operated at speeds as high as 3500 R. P. M. and is equipped with a sensitive hydraulic pressure regulating system, air and water cooling systems and means for measuring the A steel ball is immersed in the test composition which is maintained at a temperature range of from 105 C. to 130 C. for a 30-day period during which time the condition of the steel ball and test composition is observed periodically. The results obtained with compositions tested are tabulated below:

Mineral oil containing the following additives in the amount indicated:

Additive gf g Thermal Stability Results Di(2-ethylhexyl)ammo- 0.5 Passed 30-day test with no nium salt of butyl tri' sludge r COllOSlOl'l formation. chloromethane phosphonic acid. Phenyl-alpha-naphthyl- 1.0 Sludged after days.

ammonium. Oxaggline salt of olcic 1.0 Do.

ac n-decyl glycidyl ether 1.0 Sludged after 3 days. phenyl glycidyl ether 0. 5 D0. z-ethylhexanol 1. 6 D0. cyclohexauol 0. 5 Do. di-Z-tert-butyl phenol 0.5 Do. tributyl phosphite 0.2 Sludged at room temperature. dibutyl tin dilaurate. 0. 1 Sludged. lead naphthenate 0. 2 Sliidged at room temperature. calcium naphthenatc. 1.0 Sludgcd. wax disulfidc sludeed at room temperature. no stabilizing agent Do.

To compositions of this invention can be added other additives such. as blooming agents, pour point depressors and/or viscosity improvers, antifoaming agents and the like. Among the specific additives for lubricating purposes which are suitably used are oil-soluble detergents which include oil-soluble salts of various bases with detergent-forming acids. Such bases include metal as Well as organic bases. Metallic bases include those of alkali metals, Ca, Mg, Cu, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Examples of detergent-forming acids are the various fatty acids of, say, 10 to 30 carbon atoms, wool fat acids, paraffin wax acids (produced by oxidation of paraflin wax), chlorinated fatty acids, aromatic hydroxy fatty acids, paraflln wax benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkylphenol) sulfides and disulfides, methylene bis-alkyl phenols; sulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or highboiling petroleum oils with sulfuric acid; sul-.

furic acid monoesters; arsenic and antimony acid mono and diesters, and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thiophosphate diester; the alkaline earth diphenolates, specifically the calcium and barium salts of diphenol mono and polysulfldes.

Non-metallic detergents include compounds such as the phosphatides such as lecithin and oephlin, certain fatty oils as rapeseed oils, volaent purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% by weight, expressed as sulfate ash, i. e., its calcium equivalent of calcium sulfate. Also, alkaline earth metal salts of alkyl phenol-aldehyde condensation reaction products are excellent detergents.

Antioxidants comprise several types, for example, alkyl phenols such as 2,4,6-trimethyl phenol, 2,4-dimethyl-G-tertiary-butyl phenol, 2,6-ditertiary-butyl-4-methyl-phenol, and the like; amino phenols as benzyl amino phenols; amines such as dibutylphenylene diamine, diphenyl amine, phenyl beta-naphthyl-amine, phenyl-alpha-naphthylamine and dibutylaminc.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms, e. g. octadecenylsuccinic acid; alkali metal and alkaline earth metal salts of sulfonic acids and fatty acids organic compounds containing an acidic radical in close proximity to a mercapto, nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Additional ingredients may comprise oil-soluble urea or thlourea derivatives, e. g. urethanes, allophanates; carbazides, carbazons, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols; sulfurized sperm oil, sulfonized lard oil, sulfurized mineral oil, colloidal sulfur and other high molecular weight oil-soluble sulfur compounds.

Depending upon the additional additives used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to

0.5% in combination with reaction products of this invention.

We claim as our invention:

1. A lubricating composition of matter cemprising essentially a major amount of a lubricating oil and a minor amount sufficient to impart extreme pressure properties to said medium of a salt represented by the formula:

1 x,..a R-P A xrr wherein A is an oil-soluble secondary amine containing from 10 to 36 carbon atoms, R is a polyhalogenated hydrocarbyl radical containing from 1 to 8 carbon atoms, R is selected from the group consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl, and cycloalkyl radical, m is a number selected from zero and one and each X is an' oxy en.

2. A lubricating composition of matter comprising essentially a major amount of lubricating oil and a minor amount sufiicient to impart extreme pressure properties to said oil of an oilsoluble secondary aliphatic ammonium salt of a polyhalo phosphorus compound selected from the group consisting of a polyhaloalkanephosphono and polyhaloalkanephosphino, said ammonium compound containing from 10 to 36 carbon atoms and the polyhaloalkane radical containing from 1 to 8 carbon atoms.

3. A lubricating composition of matter com prising essentially a major amount of lubricating oil and a minor amount sufficient to impart extreme pressure properties to said oil of an oilsoluble secondary aliphatic ammonium salt of polyhaloalkanephosphonic acid said ammonium compound containing from 10 to 36 carbon atoms and the polyhaloalkane radical containing from 1 to 8 carbon atoms.

4. A lubricating composition of matter comprising essentially a major amount of lubricating oil and a minor amount sufficient to impart extreme pressure properties to said oil of an oilcarbon atoms and the polyhaloalkane radical containing from 1 to 8 carbon atoms.

6. A lubricating composition of matter comprising essentially a major amount of lubricating oil and a minor amount suflicient to impart extreme pressure properties to said oil of an oilsoluble secondary aliphatic ammonium salt of alkyl polyhaloalkanephosphonic acid said ammonium compound containing from 10 to 36 carbon atoms and the polyhaloalkane radical containing from 1 to 8 carbon atoms.

'7. A lubricating composition of matter comprising essentially a major amount of lubricat-' ing oil and a minor amount suflicient to impart extreme pressure properties to said oil of an oilsoluble secondary aliphatic ammonium salt of alkyl polyhaloalkanephosphonic acid said ammonium compound containing from 10 to 36 carbon atoms and the polyhaloalkane radical containing from 1 to 8 carbon atoms.

8. A lubricating composition of matter comprising essentially a major amount of lubricating oil and a minor amount suflicient to impart extreme pressure properties to said oil of an oilsoluble secondary aliphatic ammonium salt of alkyl polychloroalkanephosphonic acid said ammonium compound containing from 10 to 36 carbon atoms and the polychloroalkane radical containing from 1 to 8 carbon atoms.

9. A lubricating composition of matter comprising essentially a major amount of mineral lubricating oil and a minor amount sufficient to impart extreme pressure properties to said oil of an oil-soluble secondary aliphatic ammonium salt of alkyl po1ychloroalkanephosphonic acid said ammonium compound containing from 10 to 36 carbon atoms and the polychloroalkane radical containing from 1 to 8 carbon atoms.

10. A lubricating composition of matter comprising essentially a major amount of mineral oil and a minor amount of suificient to impart extreme pressure properties to said oil of di-Z- ethylhexyl ammonium salt of butyl trichloromethanephosphonic acid.

11. A lubricating composition of matter comprising essentially a major amount of mineral oiland a minor amount sufficient to impart extreme pressure properties to said oil of di-Z-ethylhexyl ammonium salt of trichloromethanephosphonic acid.

12. A lubricating composition of matter comprising essentially a major amount of mineral oil and a minor amount sufiicient to impart extreme pressure properties to said oil of dioctadecylammonium salt of butyl trichloromethancphosphonic acid.

13. A lubricating composition of matter comprising essentially a major amount of mineral oil and a minor amount sufficient to impart extreme pressure properties of said oil of di-2-ethylhexyl ammonium salt of ethyl trichlorometlianephosphonic acid.

14. A lubricating composition of matter comprising essentially a major amount of mineral lubricating oil and a minor amount sufiicient to impart extreme pressure properties to said oil of di-2-ethylhexyl ammonium salt of butyl trichloromethanephosphonic acid.

15. A lubricating composition of matter comprising essentially a major amount of mineral lubricating oil and a minor amount suiiicient to impart extreme pressure properties of said 021 of dioctadecylammonium salt of butyl trichloromethanephosphonic acid.

16. A lubricating composition of matter comprising essentially a major amount of cii-2-ethylhexyl sebacate and a minor amount sufficient to impart extreme pressure properties to said oil of di-Z-ethylhexyl ammonium salt of butyl trichloromethanephosphonic acid.

1'7. A lubricating composition of matter comprising essentially a major amount of di2-ethylhexyl sebacate and a minor amount suificient to impart extreme pressure properties to said oil of dioctadecylammonium salt of butyl trichloromethanephosphonic acid.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,311,306 Ritchey Feb. 16, 1943 2,400,611 Smith et a1 May 21, 1946 2,573,568 Harman et al Oct. 30, 1951 

1. A LUBRICATING COMPOSITION OF MATTER COMPRISING ESSENTIALLY A MAJOR AMOUNT OF A LUBRICATING OIL AND A MINOR AMOUNT SUFFICIENT TO IMPART EXTREME PRESSURE PROPERTIES TO SAID MEDIUM OF A SALT REPRESENTED BY THE FORMULA 